Iodination or hydroiodination of alkylene bisamide-containing polypropylene fibers dyd with basic dyes



United States Patent 3,394,984 IODINATIUN 0R HYDROIODINATION 0F ALKYL-ENE BISAMHDE-CONTAININ G POLYPROPYLENE FIBERS DYED WITH BASIC DYES AlrioKoshimo and Hirohisa Nara, Uji-shi, Kyoto-tn,

Japan, assignors to Nippon Rayon Co., Ltd., Kyotofu, Japan No Drawing.Continuation of application Ser. No. 251,487, Jan. 15, 1963. Thisapplication Feb. 7, 1967, Ser. No. 614,518

6 Claims. (Cl. 8-31) The present application is a continuation of S.N.251,- 487, filed Jan. 15, 1963, now abandoned.

The present invention relates to a process for improving the lightfastness of dyed polymeric olefines.

In general, brilliant shades are obtained by basic and cation dyestuffs,but the light fastness of the dyed products is not satisfactory.Accordingly, when above dyestuffs are used, dyed synthetic fibres andother articles formed of polymeric olefines possess extremely low lightfastness, so that these dyestuffs cannot be used in practice.

As the result of extensive investigations to improve the light fastnessof polymeric olefines which are dyed with basic and cation dyestuffs andto bring these dyed polymeric olefines into practical use, it has nowbeen found that the addition of iodine into a dyebath or theaftertreatment of dyed polymeric olefines with iodine or with hydrogeniodide provides a marked improvement in the light fastness of polymericolefines which are dyed with above dyestuffs and also acid dyestuffs.

According to the feature of the present invention, a process forimproving the light fastness of dyed polymeric olefines comprises dyeingthe polymeric olefines in a dye bath containing iodine or hydrogeniodide as an auxiliary agent.

According to the another feature of the present invention, therefore, aprocess for improving the light fastness of dyed polymeric olefinescomprises after-treating the dyed polymeric olefines with iodine orhydrogen iodide.

The method for improving the dyeing properties of polyolefine fibres bytreating them with iodine is known, but in the present invention iodineis used for improving the light fastness of dyed polymeric olefineswhich are dyed with basic, cation or acid dyestuffs.

Consequently, the present invention is different from the prior methodfor the pre-treatment of polymeric olefines with iodine in that theobject of the present invention is to improve the light fastness of thedyed product and the object of the prior method is to improvedyeability.

The synthetic fibres and other articles herein referred to as beingformed of polymeric olefines included those produced of polyolefinesalone, mixtures of polyolefines and other polymers, mixtures ofpolyolefines and organic compounds having lower molecular weight, graftpolymers based on polyolefines, and copolymers of polyolefines withother compounds.

Treatments with other halogens and halogenides except iodine andhydrogen iodide give little effect to improve the light fastness ofpolymeric olefines dyed with basic and cation dyestuffs. Further,treatments with other compounds which are known as lightproof agentssuch as benzophenone, benztriazol and their derivatives give also noeffect to improve the light fastness of polymeric olefines dyed withbasic, cation or acid dyestuffs.

Although the mechanism how the light fastness of dyed polymeric olefinestreated with iodine or hydrogen iodide is improved is not clear, it maybe considered that iodine or hydrogen iodide in said fibres or otherarticles absorbs energy of sunlight and prevent the decomposition ofbasic, cation dyestuffs, etc.

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In case iodine or hydrogen iodide is used as an auxiliary agent duringdyeing process in the present invention, for example, synthetic fibresor other articles based on polymeric olefines are dyed in a bathcontaining requisite amounts of basic dyestuff and 05-15 of iodine basedon the weight of fibres. In this case, iodine is previously dissolvedwith a suitable solvent, and then added to the dye bath. Dyeing iscarried out at a given pH and 100 C. for 0.5-2 hours, and the dyedpolymeric olefines obtained have very excellent light fastness.

In case dyed polymeric olefines are subjected to the after-treatmentwith iodine or hydrogen iodide in the present invention, for example,synthetic fibres or other articles formed of polymeric olefines dyedwith basic or cation dyestuffs are treated in the bath, in which iodineor hydrogen iodide is dissolved in water, alcohol, chloro form or anaqueous solution of potassium iodide, at a temperature higher than roomtemperature for from several minutes to 2 hours and then rinsedsufliciently. Further, this treatment can be carried out in iodine orhydrogen iodide vapour.

The present invention can be applied in case the polymeric olefines aredyed with basic, cation or acid dyestuffs after chemical treatment, suchas chlorination, sulfonation and acid and amine treatments.

The light fastness of dyed polymeric olefines subjected to theafter-treatment is outstandingly superior into that of the untreatedproducts. For example, if the light fastness of polymeric olefines dyedwith basic dyestuffs is only grade 1 according to AATCC test whenuntreated, it becomes grade 4, 5, 6 or higher after being treated inaccordance with one of the processes described above.

The following examples serve to illustrate the present invention, butthey are not intended to limit it thereto.

EXAMPLE 1 Crystalline polypropylene material having an average molecularweight of 77,000 was blended with 3% by weight of octadecylamine andmethylene bis-stearamide respectively and subsequently drawn at a drawratio of 5 after being melt-spun at 240 C. The resulting fibre wastreated with a bath of 20% hydrochloric acid solution at 100 C. for 30min., neutralized with sodium carbonate solution and then rinsed withcold water sufficiently. The fibre, thus treated, was dyed in a weakalkaline bath containing the basic or cation dyestuffs described inTable I -at 100 C. for 60 min. After being treated in a bath containing5% (based on the weight of fibres) of iodine dissolved in 10 g./l.aqueous potassium iodide solution at C. for 30 min., the dyed materialswere rinsed sufficiently and then soaped.

The light fastness of the dyed materials after the above treatment withiodine was greatly improved in comparison with untreated materials asshown in Table I. The light fastness values in Table I are estimated byAATCC test using a Fade-Ometer.

TABLE I Light fastness Light of dyed fastness Dyestulls materials ofdyed treated materials with untreated iodine (class) (class) Auromine(0.1. Basic Yellow 2) 0.1. 41,000. 4 1 Astra Phloxine FF cone. (0.1.Basic Red 12) 0.1. 48,070 5 1 Malachite Green (0.1. Basic Green 4) 0.1.

4,200 4 1 Victoria Pure Blue BOH (0.1. Basic Blue 7) 0.1. 42,595 4 1Crystal Violet (0.1. Basic Violet 3) 0.1. 42,555- 5 2 Astrazon YellowGRL 5 2 Asrpzon Orange R (0.1. Basic Orange 22) 4 1 Astrazon Black M 5 13 EXAMPLE 2 Crystalline polypropylene material having an averagemolecular weight of 77,000 was blended with by weight of polyetheresterresin prepared from mixture of hydroxy benzoic acid, dimethylterephthalate and ethylene glycol, and subsequently drawn at a drawratio of 5, after being melt spun at 270 C.

The fibre thus obtained was dyed in a weak alkaline bath containing 5%(based on the weight of fibre) of iodine dissolved in g./l. of potassiumiodide solution and basic and cation dyestuffs described in Table II at100 C. for 60 min.

The light fastness of the materials thus dyed was greatly improved incomparison with materials dyed without the addition of iodine to the dyebath as shown in Table II. The light fastness values in Table II areestimated by AATCC test using a Fade-Ometer.

EXAMPLE 3 After being treated with solution containing calciumhypochlorite and hydrochloric acid, polypropylene fibre was dyed in aweak alkaline bath containing basic or cation dyestuffs, as shown inTable III. The dyed material was subsequently treated in an aqueoussolution of 5% of iodine (based on the weight of the fibres) and ofpotassium iodide (based on the weight of the fibres) at 90 C. for min.,rinsed sufficiently and soaped.

The light fastness of the dyed materials, after being treated asdescribed above, was greatly improved in comparison with untreated dyedmaterials as shown in Table III. The light fastness values in Table IIIare estimated by AATCC test using a Fade-Ometer.

What is claimed is: i

1. A process for improving the light fastness of polypropylene fibersblended with an alkylene bis-fatty acid amide dyed with a basic dyestufiwhich comprises treating said fibers with an aqueous solution containing0.5- 15% of iodine or hydrogen iodide.

2. A process according to claim 1, in which said polypropylene fibersare treated with said solution during dyeing with the basic dyestuff.

3. A process according to claim 1, in which said polypropylene fibersare treated with said solution after dyeing with the basic dyestutf.

4. A process according to claim 1, further comprising treating saidpolypropylene fibers with an aqueous solution of potassium iodide duringapplication of said iodine or hydrogen iodide solution.

5. A process according to claim 4, in which the concentration ofpotassium iodide in said aqueous solution is 10 grams per liter.

6. A process according to claim 1, in which, when said member of saidgroup is iodine, the concentration thereof in said solution is from05-15% based on weight of polypropylene fibers.

References Cited UNITED STATES PATENTS 2,276,951 5/1942 Fisher 2051632,537,627 1/1951 Weissart et a1. 260-457 2,805,960 9/ 1957 Wolinski117--38 2,931,296 4/1960 Ryan et al. 8-100 FOREIGN PATENTS 1,083,6516/1960 Germany.

OTHER REFERENCES Meili: American Dyestuff Reporter, May 1948, pages81-83,TP890 512.

Diserens: Chemical Technology of Dyeing and Printing, vol. 2, page 84,pub. 1951 by Reinhold Pub. Corp, N.Y.C. TP893D49.

Venkataramann: The Chemistry of Synthetic Dyes, vol. I, page 69, pub.1952 by Academic Press Inc., N.Y.C. TP913V4C2.

Finch: Fibers and Plastics, January 1960, pages 14-16.

Musgrave: Fibers and Plastics, August 1960, pages 241244.

Strobel et al.: American Dyestulf Reporter, Aug. 7, 1961, pages 583-585.

NORMAN G. TORCHIN, Primaly Examiner.

DONALD LEVY, Assistant Examiner.

1. A PROCESS FOR IMPROVING THE LIGHT FASTNESS OF POLYPROPYLENE FIBERSBLENDED WITH AN ALKYLENE BIS-FATTY ACID AMIDE DYED WITH A BASIC DYESTUFFWHICH COMPRISES TREATING SAID FIBERS WITH AN AQUEOUS SOLTUTIONCONTAINING 0.515% OF IODINE OR HYDROGEN IODIDE.